JP4589116B2 - Acid Red 82 in the mixture - Google Patents

Abstract

The invention relates to mixtures containing the dye C.I. Acid Red 82 (formula IIb) and C.I. Acid Red 80 (formula IIc)

Description

  The present invention relates to a mixture of Acid Red 82 and Acid Red 80, methods for their production and their use in printing inks suitable for ink jet methods. The corresponding printing inks of color magenta have a surprisingly high long-term stability, whereby very high light and ozone resistances and prints of suitable shades can be produced.

  The ink jet method is understood to be an ink jet recording method in which small droplets of writing liquid (ink) are sprayed onto a substrate (paper, fabric, plastic, metal) from a small nozzle. The droplets are grouped into letters or graphics by electronic control. Fine ink droplets can be produced by different methods; preferably, generally known continuous methods and drop-on-demand methods (thermal ink jet, bubble jet, piezo ink jet) are used.

  From EP-A-1 123 932 it is known to use an anthrapyridone derivative as a magenta dye in an ink jet process which is distinguished by a particularly high light and ozone resistance. In particular, there is a general formula (I)

［式中、
Ｒ′はＨ又はアルキルを表し；
Ｒ″はＨ、アルキル、ＯＰｈ、ＳＯ_３Ｈ又はＣＯＯＨを表す（Ｐｈ＝フェニル）］
で示されるタイプの染料が適しているとして記載されている。

[Where:
R ′ represents H or alkyl;
R ″ represents H, alkyl, OPh, SO ₃ H or COOH (Ph = phenyl)]
The dyes of the type indicated are described as being suitable.

  Substituents X and Y are used mainly as substituents X and Y which give rise to an increased solubility of the dye in aqueous solution. However, the advantage of increased solubility is clearly accompanied by a reduced color intensity. Moreover, relatively high synthesis costs are required to produce the dye.

  A similar high light and ozone resistance, as in the case of type I dyes, and thus an apparently higher color strength, already has structurally simpler anthrapyridones such as C.I. I. Provided from Acid Red 82 (Formula IIb).

［式中、
ａ）Ｒ^１＝Ｈ；Ｒ^２＝ＳＯ_３Ｈ：アシッドレッド８１
ｂ）Ｒ^１＝ＳＯ_３Ｈ；Ｒ^２＝ＳＯ_３Ｈ：アシッドレッド８２
ｃ）Ｒ^１＝ＳＯ_３Ｈ；Ｒ^２＝ＣＨ_３：アシッドレッド８０
を表す］
前記染料は、例えばDE-A-2 543 092、DE-A-3 220 334及びEP-A-1 048 705にインクジェット法における使用のために既に個々に記載されている。

[Where:
a) R ¹ = H; R ² = SO ₃ H: Acid Red 81
b) R ¹ = SO ₃ H; R ² = SO ₃ H: Acid Red 82
c) R ¹ = SO ₃ H; R ² = CH ₃ : Acid Red 80
Represents]
Said dyes have already been described individually for use in ink jet processes, for example in DE-A-2 543 092, DE-A-3 220 334 and EP-A-1 048 705.

  However, the dye C. I. The practical use of Acid Red 82 could not be realized so far because sufficient long term stability could not be achieved in ink formulations used for inkjet printing. . In addition, the color tone of the aqueous ink solution of Acid Red 82 printed by the ink jet method is more reddish than the dye solution normally used in the ink set as a magenta component.

  Therefore, the object of the present invention is to provide dyes in inks commonly used in ink-jet processes, which provide a very good long-term stability in the light and ozone resistance that remains unchanged and, in some cases, a deep color shift that is additionally weak in hue. C. I. It was to provide the possibility to use Acid Red 82. Moreover, their industrial realization should not exceed the cost for manufacturing Acid Red 82.

  Surprisingly, Acid Red 82 and the anthrapyridone dye C.I. I. A mixture with Acid Red 80 (IIc) may have a clearly increased long-term stability in an ink formulation, despite the fact that Acid Red 80 has a slightly lower solubility than Acid Red 82. Found now.

  In contrast, the corresponding mixture of Acid Red 82 and Acid Red 81 resulted in a clearly worse long-term stability.

  Therefore, the present invention relates to the dye C.I. I. Acid Red 82 (Formula IIb) and C.I. I. A mixture containing Acid Red 80 (Formula IIc).

  Preferred mixtures have a mass ratio of (IIb) to (IIc) of 99: 1 to 1:99, preferably 98: 2 to 50:50, in particular 96: 4 to 70:30, very particularly preferably 95: 5. Characterized by ˜85: 15.

  The dyes of the formulas (IIb) and (IIc) are preferably present in the form of their salts, with sodium, lithium, ammonium, tetraalkylammonium, trialkanolammonium, alkyldialkanolammonium being used as cations.

  The mixtures according to the invention may be present in solid form, for example as powders or granules, and in liquid form, for example as suspensions, for example pastes or aqueous solutions.

  Particularly preferably, the mixture according to the invention is present as an aqueous solution which is likewise the subject of the invention.

  In addition to the dyes of the formulas (IIb) and (IIc), the aqueous solutions according to the invention may of course also contain further dyes, in particular for shading (Nuancieren).

  Preferably, these aqueous solutions are characterized in that 90 to 100% by weight, in particular 95 to 100, preferably 98 to 100% by weight of the dye amount consist of dyes of the formulas (IIb) and (IIc).

  The aqueous solution according to the invention is preferably 0.01-25.0% by weight, in particular 0.01-15.0% by weight, preferably 0.05-10.0% by weight of the dyes of the formulas (IIb) and (IIc). %, Particularly preferably 0.1 to 5.0% by mass. Likewise preferably they contain 25% by weight or more, in particular they contain 85 to 99.99% by weight of water and optionally a solvent, preferably 0 to 50% by weight, in particular 0 to 15% by weight and optionally further. Contains the usual ingredients.

  In a preferred embodiment, the aqueous solution according to the invention contains 5 to 25% by weight of the dye, wherein 90 to 100% by weight of the dye amount consists of the dyes of the formulas (IIb) and (IIc) and the balance is water. is there. These are used in particular as concentrates for producing inks.

  Likewise, in one preferred embodiment, the aqueous solution according to the invention contains 0.01 to 15.0% by weight of dyes of the formulas (IIb) and (IIc), preferably 0.05 to 10.0% by weight, particularly preferably 0.0. 1 to 5.0% by mass is contained. Likewise preferably they contain 0 to 50% by weight, preferably 15 to 40% by weight, of organic solvents. Such an aqueous solution is preferably used as a recording liquid (ink).

  Preferred organic solvents are those miscible with water, especially alcohols and their ethers or esters, carboxylic acid amides, ureas, sulfoxides and sulfones, especially those having a molecular weight of <200 g / mol. is there. Particularly suitable solvents are, for example: methanol, ethanol, propanol; ethylene glycol, propylene glycol, diethylene glycol, thiodiethylene glycol and dipropylene glycol; butanediol; -hydroxypropionitrile, pentamethylene glycol, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether and ethylene glycol monobutyl ether, ethylene diglycol monoethyl ether, triethylene glycol monobutyl ether, butyl polyglycol, formamide, triethylene glycol, 1,5-pentanediol, 1,3,6-hexanetriol, acetic acid -2-hydroxyethyl ester, acetic acid-2 (2'-hydroxy) -ethyl ester, glycerin Glycol acetate, 1,2-dihydroxypropane, 1-methoxy-2-propanol, 2-methoxy-1-propanol, N, N-dimethylformamide, pyrrolidone, ε-caprolactam, N-methyl-caprolactam, butyrolactone, urea, tetra Methylurea, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylolpropyleneurea, dimethylsulfoxide, dimethylsulfone, sulfolane, isopropanol, polyethylene glycol and mixtures thereof.

  Furthermore, the aqueous solution according to the present invention preferably contains as little foreign salt (Fremdsalze) as possible. Heterogeneous salts are understood in this context as being customary salts that can occur in the synthesis of dyes of the formulas (IIb) and (IIc), such as sodium chloride or potassium chloride or sodium sulfate or potassium sulfate and mixtures thereof. Should be.

  The foreign salt content is preferably <1% by weight, in particular <0.5% by weight, based on the solution.

  A correspondingly low foreign salt content can be obtained, for example, by reverse osmosis or ultrafiltration using a corresponding membrane.

The mixture according to the invention is for example
a) mixing the dyes of formula (IIb) and (IIc) with each other or b) reacting the compound of formula (III) with a mixture of anilines of formula (IVb) and (IVc) and formula (Vb) and Can be prepared by sulfone-substituting the resulting mixture of compounds of (Vc) or c) preparing compounds of formula (Vb) and (Vc) separately and sulfone-substituting into the mixture according to the invention together. it can.

  In the case of preparation variant b), 6-bromo-3-methyl-3H-dibenz [f, ij] -isoquinoline-2,7-dione of formula (III) is preferably aniline and 4-methylaniline (IVb + IVc) Calculated for the desired ratio of the final products (IIb and IIc) in a mixture consisting in particular of a temperature of 170-180 ° C. with addition of sodium carbonate, in particular in a ratio of 95.3: 4.7 And the resulting mixed dye base (Vb and Vc) is subsequently used with a sulfonating agent, for example, sulfuric acid with a 20% fraction of sulfur trioxide (20% fuming sulfuric acid) to give acid red 82 (IIb ) And acid red 80 (IIc). Preferably sulfonation is carried out at 20-40 ° C. The mixture can then be desalted by reverse osmosis and mixed with suitable solvents and auxiliaries and converted into ink for use in the ink jet process. This also applies to the mixture produced by variant c).

  In the preparation variant c), 6-bromo-3-methyl-3H-dibenz [f, ij] -isoquinoline-2,7-dione of the formula (III) and preferably aniline or 4-methylaniline (IVb or The dye bases (Va and Vb) are prepared separately by reaction with IVc), mixed in the ratio calculated for the desired ratio of the final product, and further sulfone substituted as described above.

By a separate reaction, product Acid Red 82 (IIb) and Acid Red 80 (IIc) can be produced by option a) and mixed in a ratio calculated for the desired ratio of the final product. Can. After possible desalting, the solution can then be further mixed with suitable solvents and auxiliaries and converted into ink for use in the ink jet process.
Option b) is preferably used.

  As auxiliary agents, for example, dissolution aids, dispersants, wetting agents, biocides or buffer systems are considered. The proportion of these components is usually 0-10% by weight, preferably 0-5% by weight, based on the weight of the formulation.

In the use of the dye mixture according to the invention in the form of an aqueous solution as a recording liquid for an ink jet recording system, C.I. I. The following advantages are provided compared to the use of Acid Red 82:
A high long-term stability of the ink formulation is achieved in relation to changes in physical properties and deposit formation;
The color tone of the ink formulation printed in the ink jet process is shifted to a deep color;

The following advantages of using a single dye remain unchanged:
The extremely high light and ozone resistance of the printed matter obtained in the ink jet process is achieved;
-There is a higher color intensity compared to the more complexly structured anthrapyridone dyes of the formula I;
The production of the dye mixture is associated with a relatively low synthesis cost, which corresponds only to the cost of producing a single dye.

  The following examples should explain the invention in more detail. The description of a part is a mass part.

Example 1 (Acid Red 82)
C. I. To produce Acid Red 82, 180 parts of 150 parts of aniline, 12 parts of sodium carbonate and 60 parts of 6-bromo-3-methyl-3H-dibenz [f, ij] -isoquinoline-2,7-dione (III) For 4 hours,

その際に遊離した水を、水分離器を用いて反応から除去した。８０℃に冷却した後に、メタノール１２０部を添加し、室温に冷却し、吸引ろ過し、メタノール４０部で洗浄した。残留物を水１５０部中でスラリーにし、濃塩酸で１のｐＨ値に調節し、８０℃で１ｈ熱処理した。引き続いて吸引ろ過し、水で洗浄し、かつ乾燥させた。

The water liberated in this case was removed from the reaction using a water separator. After cooling to 80 ° C., 120 parts of methanol was added, cooled to room temperature, suction filtered, and washed with 40 parts of methanol. The residue was slurried in 150 parts of water, adjusted to a pH value of 1 with concentrated hydrochloric acid and heat treated at 80 ° C. for 1 h. Subsequently, it was suction filtered, washed with water and dried.

  The obtained paste (65 parts) was mixed little by little into 210 parts of fuming sulfuric acid 20% so that the temperature did not exceed 40 ° C., and stirred at 40 ° C. for 16 hours. Thereafter, the reaction mixture was taken out on 800 parts of ice, suction filtered, and washed with dilute hydrochloric acid. The wet presscake was dissolved in 300 ml of distilled water, adjusted to a pH value of 7.5 with caustic soda solution, and desalted to a salt content of less than 0.1% by weight using reverse osmosis. . Subsequently, the final volume was adjusted to 890 mL with distilled water. The aqueous dye solution thus obtained contains 10% by mass of pure dye Acid Red 82.

Example 2 (Acid Red 80)
C. I. To make Acid Red 80, the same procedure was used as in Example 1, but 170 parts of 4-methylaniline were used instead of 150 parts of aniline. After desalting using reverse osmosis, the final volume was adjusted to 760 mL with distilled water. The aqueous dye solution thus obtained contains 10% pure dye Acid Red 80.

Example 3
In order to produce a mixture according to the invention of the components Acid Red 82 and Acid Red 80 in a ratio of 90:10 with respect to the mass% of pure dye, the same procedure was followed as in Example 1, but instead of 150 parts of aniline. A mixture consisting of 143 parts of aniline and 7 parts of 4-methylaniline was used. After desalting using reverse osmosis, the final volume was adjusted to 870 mL with distilled water. The aqueous dye solution thus obtained contains 10% pure dye as a mixture of Acid Red 82 and Acid Red 80.

Example 4 (comparative example)
In order to produce an ink suitable for the inkjet process, the following ingredients were mixed together and filtered through a cellulose nitrate filter with a pore size of 0.2 μm. The ink formulation is similar in composition to conventional printing inks as disclosed, for example, in EP-A 1048705.

C. from Example 1 I. Acid Red 82 dye solution 30 parts distilled water 35 parts glycerin 5 parts diethylene glycol 15 parts diethylene glycol monobutyl ether 5 parts 1,3-dimethylimidazolidin-2-one 5 parts N, N-dimethylurea 5 parts In this ink formulation, Precipitation was observed after 8 weeks storage time at room temperature and independently after 20 days storage time at 50 ° C.

Example 5 (comparative example)
The same operation as in Example 4 was carried out except that the C.I. I. Using Acid Red 80 dye solution, precipitation was observed in the ink formulation after 6 weeks storage time at room temperature and independently after 20 days storage time at 50 ° C.

Example 6 (comparative example)
The same operation as in Example 4 was carried out, however, with a 90:10 ratio of C.I. I. Using a 10% dye solution of Acid Red 82 and Acid Red 81, precipitation was observed in the ink formulation after 2 weeks storage time at room temperature and independently after 5 days storage time at 50 ° C.

Example 7
Operating in the same way as in Example 4, however, using the dye solution according to the invention prepared according to Example 3, any kind of precipitation is observed at room temperature or after 6 months storage time at 50 ° C. I could not.

  Apart from that, the same was observed when both dyes were not manufactured together but were mixed after separate manufacturing and the mixture was used.

Claims (15)

Dye C.I. I. Acid Red 82 (Formula IIb) and C.I. I. A mixture containing Acid Red 80 (Formula IIc).

The weight ratio of (IIb) and (IIc) is 99: 1 to 1: 9 is 9, claim 1 mixture according. The mixture of Claim 1 or 2 whose mass ratio of (IIb) and (IIc) is 98: 2-50: 50. The mixture according to any one of claims 1 to 3, wherein a mass ratio of (IIb) to (IIc) is from 96: 4 to 70:30. The mixture according to any one of claims 1 to 4, wherein the mass ratio of (IIb) to (IIc) is 95: 5 to 85:15. There the dye is in the form of their salts, sodium as the cation in this case, lithium, ammonium, tetraalkylammonium, trialkanolammonium, alkyl di alkanolammonium used, either of claims 1 to 5 1 The mixture according to item. An aqueous solution containing the mixture according to any one of claims 1 to 6 . The aqueous solution according to claim 7 , wherein 90 to 100% by mass of the dye amount comprises the dyes of the formulas (IIb) and (IIc). The aqueous solution according to any one of claims 7 to 8 , wherein the dye content of the dyes (IIb) and (IIc) is 0.01 to 15.0 mass% with respect to the mass of the aqueous solution. The organic solvent has 0-50 wt% including, aqueous solution of any one of claims 7 to 9. The aqueous solution according to any one of claims 7 to 10, comprising 15 to 40% by mass of an organic solvent. A method for producing a mixture according to claim 1,
wherein the <br/> that you mixing a) expression of dye (IIb) and (IIc) from each other, The method according to claim 1 mixture according. A method for producing a mixture according to claim 1,
b) Formula (III)

Compounds represented by formula (IVb) and (IVc)

And a mixture of anilines of formula (Vb) and (Vc)

Sulfonate the resulting mixture of compounds
The method for producing a mixture according to claim 1. A method for producing a mixture according to claim 1,
c) Formulas (Vb) and ( Vc)

A process for producing a mixture according to claim 1, characterized in that the compounds of formula (1) are prepared separately and sulfonated together. Use of the aqueous solution according to any one of claims 7 to 11 as a recording liquid (ink) for inkjet printing.